Ethyl bromopyruvate → (2S,4R)-2-(4-carboxythiazol-2-yl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl) pyrrolidine

HRID 846949

Reaction equation

HRID 846949 reaction equation
[CH3:1][S:2]([O:5][C@H:6]1[CH2:10][N:9]([C:11]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=2)=[O:12])[C@H:8]([C:24](=[S:26])[NH2:25])[CH2:7]1)(=[O:4])=[O:3].Br[CH2:28][C:29](=O)[C:30]([O:32]CC)=[O:31]>ClCCl.C(O)C>[C:30]([C:29]1[N:25]=[C:24]([C@@H:8]2[CH2:7][C@@H:6]([O:5][S:2]([CH3:1])(=[O:4])=[O:3])[CH2:10][N:9]2[C:11]([O:13][CH2:14][C:15]2[CH:16]=[CH:17][C:18]([N+:21]([O-:23])=[O:22])=[CH:19][CH:20]=2)=[O:12])[S:26][CH:28]=1)([OH:32])=[O:31]

Participants

5

Reactant 2

HCID 66144Ethyl bromopyruvateHCID 14305069(2S, 4R)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)-2-thiocarbamoylpyrrolidine

Product 1

HCID 18638791(2S,4R)-2-(4-carboxythiazol-2-yl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl) pyrrolidine

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of (2S,4R)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)-2-thiocarbamoylpyrrolidine (2.0 g) in dichloromethane (40 ml) was added a solution of ethyl bromopyruvate (1.04 ml) in absolute ethanol (10 ml) at 0° C. After stirring at room temperature for 2 hours, the mixture was evaporated. The residue was dissolved in ethyl acetate, and washed with saturated sodium bicarbonate and brine successively. The dried organic layer was evaporated and the residue was dissolved in tetrahydrofuran (15 ml) and 1N sodium hydroxide (15 ml). After stirring at 35°-45° C. for 1 hour, the mixture was evaporated and poured into ethyl acetate. To this mixture was added 1N hydrochloric acid (20 ml), and then organic layer was separated, and washed with brine. The dried organic layer was evaporated to give (2S,4R)-2-(4-carboxythiazol-2-yl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (1.54 g).

Workup

  1. customthe mixture was evaporated
  2. dissolutionThe residue was dissolved in ethyl acetate
  3. washwashed with saturated sodium bicarbonate and brine successively
  4. customThe dried organic layer was evaporated
  5. dissolutionthe residue was dissolved in tetrahydrofuran (15 ml)
  6. stirringAfter stirring at 35°-45° C. for 1 hour
  7. customthe mixture was evaporated
  8. additionpoured into ethyl acetate
  9. additionTo this mixture was added 1N hydrochloric acid (20 ml)
  10. customorganic layer was separated
  11. washwashed with brine
  12. customThe dried organic layer was evaporated

Sources & evidence

ORD record
ord-41d586b093454ef4828ef01825e9453a
Source dataset
uspto-grants-1992_08
Patent number
US05138064

Linked notes

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